Dithiepanyl anilids

ABSTRACT

This invention discloses new compounds of the formula   WHEREIN Y is selected from the group consisting of hydrogen, lower alkyl and halogen; R1 is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R2 is lower alkyl; R3, R4, R5, R6 and R7 are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen; m is an integer from 0 to 2; Z1 and Z2 are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2. The compounds of the above description are useful as herbicides.

United States Patent [1 1 Richter et al. July 8, 1975 DITHIEPANYL ANILIDS [75] lnventors: Sidney B. Richter, Chicago; John Krenzer, Oak Park, both of I11. 4

R [73] Assignee: Velsicol Chemical Corporation,

Chicago, Ill. c 22 Filed: June 3, 1974 (c15 cu (c11 [21] App]. No: 475,547 2 6 N Z C R Related U.S. Application Data 7 [62] Division of Ser. No. 357,746, May 7, 1973. fi R 3 52 us. ca 260/327 M l O P 51 Int. Cl c070 75/00 R [58] Field of Search 260/327 M [56] References Cited wherein Y is selected from the group consisting of hy- UNITED STATES PATENTS drogen, lower alkyl and halogen; R is selected from 3,759,952 9/1973 Teach 260/327 the group Consisting of hydrogen, lower alkyl and 3,772,334 11/1973 Teach 260/327 lower alkoxy; R is lower alkyl; R R R R and R Primary ExaminerHenry R. .liles Assistant ExaminerC. M. S. Jaisle Attorney, Agent, or FirmRobert .l. Schwarz; Dietmar l-l. Olesch [57] ABSTRACT This invention discloses new compounds of the formula are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen; m is an integer from O to 2; Z and Z are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2. The compounds of the above description are useful as herbicides.

2 Claims, No Drawings DITHIEPANYL ANILIDS This application is a divisional application of our copending application, Ser. No. 357,746, filed May 7, 1973.

This invention relates to new compositions of matter 5 and more specifically relates to new compounds of the formula wherein Y is selected from the group consisting of by drogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R is lower alkyl; R R R R and R are inde pendently selected from the group consisting of hydrogen and lower alkyl; X is halogen, m is an integer from to 2; Z and Z are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2.

The term lower as used herein designates a straight 30 or branched carbon chain of up to 4- carbon atoms.

The compounds of the present invention are unexpectedly useful as herbicides and are particularly useful in controlling grassy weeds.

35 In a preferred embodiment of the present invention Y is hydrogen, X is chlorine or bromine, and at least two of R R R and R are hydrogen.

The compounds of the present invention can be prepared by reacting a compound of the formula wherein Y, R, R R R R R Z, Z 11 and m are as heretofore described, with an a-haloalkanoyl chloride of the formula Cl-C-CHX wherein X and R are as heretofore described. This reaction can be effected by combining a compound of formula ll with a compound of formula Ill in an inert 65 organic reaction medium, such as dioxane, in the presence of an acid acceptor, such as an alkali metal carbonate or bicarbonate at a temperature of from about C to about C and stirring the resulting mixture for a period of about 15 to about 120 minutes. After (Ill) this time the reaction mixture can be washed with water to remove inorganic salts and stripped of solvent to yield the desired product. This product can be used as such or can be further purified by recrystallization of other conventional means.

The compounds of formula II can be prepared by reacting a substituted aniline of the formula wherein Y, R and R are as heretofore described, with a compound of the formula wherein Hal designates halogen such as chlorine or bromine and wherein Z, Z R R R R n and m are as heretofore described. This reaction can be effected by combining a compound of formula IV with a compound of formula V in an inert organic reaction mix ture such as dimethylformamide in the presence of an acid acceptor such as an alkali metal carbonate or bicarbonate and heating the resulting mixture at reflux for a period of from about 4 to about 48 hours. After this time the reaction mixture can be filtered and distilled to yield the desired product.

The compounds of formula V can be prepared by reacting an acetal of the formula OCH wherein n is as heretofore described, with a diol or dithiol of the formula described. This reaction can be effected by combining the compound of formula VI with the compound of formula Vll in about equimolar amounts and in the presence of an acid catalyst, such as sulfuric acid or toluene sulfonic acid, under anhydrous conditions. The mixture can be heated at reflux for a period of from about 1 to about 4 hours. After this time the reaction mixture can be distilled under reduced pressure to yield the desired product.

. Exemplary diols and dithiols of formula Vll useful for preparing the compounds of formula V are ethandiol- 1,2, propandiol-l ,2, propandiol-l ,3, butandiol-l,2,

' butandiol-l,3, butandiol-l,4, butandiol-2,3, pentandiol-l,2, pentandiol-l,3, pentandiol-l,4, pentandiol-2,3, pentandiol-2,4, 2-methylpentandiol-2,4, 2-methylpropandiol-l ,2, 2-methylbutandiol-2,3, 3-methylbutandiol-l,3, hexandiol-l,2, hexandiol-l,3, hexandiol-1,4, hexandiol-2,3, hexandiol-2,4, hexandiol-2,5, hexandidioxolane (25 grams), potassium'carb'onate (34 grams) and dimethylformamide' (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture m heated at reflux for aj'period of about 18 hours. After this time the mixture was filtered and distilled to yield the desiredproduct N-(l,3-dioxolan-2- ylmethyl)-2,6-dimethylaniline.

ol-3,4, 3-methylhexandiol-3,4, 3-ethylhexandiol-3,4,'

ethandithiol-l ,2, propandithioll ,2, propandithioll ,3

butandithiol-J ,2, butandithioll ,3, butandithioll ,4,

butandithiol-2,3, pentandithiol-l,2 and the like.

Exemplary substituted anilines of formula IV useful for preparing the compounds of formula II are 2- The preparation of the compounds of the present in-' vention is more specifically illustrated in the following examples.

EXAMPLE 1 Preparation of Z-Chloromethyl-l,3-dioxolane The dimethyl acetal of 2 -chloroacetaldehyde (125 grams; 1.0 mole) and ethandiol-l,2 (62 grams, 1.0 mole) are charged into a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux con- EXAMPLE 3 Preparation of N-a-Chloroacetyl-N-( 1,3-dioxolan-2-ylmethyl)-2,6- dimethylaniline N-( 1 ,3-Dioxolan-2-ylmethyl)-2,6-dimethylaniline (7.8 grams), sodium bicarbonate (7.0 grams), dioxane (20 ml) and water (4 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture was cooled to a temperature of about 0C and chloroacetyl chloride (5.0 grams) was added, with stirring, over a period of about 15 minutes. After the addition was completed stirring ,was contin-f ued for a period of about 1 hour. After this time ether 100 ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and. stripped of solvents leavingasolid residue-The residue was recrystallized from an ether-pentane mixture to yield the desired product N-a-chloroacetyl-IN-(1,3 having a dioxolan-2-ylmethyl)-2,6-dimethylaniline melting point of 58 to 60C.

EXAMPLE 4 preparation of N-( l ,3-Dioxolan-2-ylmethyl)-2,6-diethylaniline 2,6-Diethylaniline gramsj 0.5 mole 2-chloromethyl-l,3-dioxolane (25 grams; 0.2 mole),

potassium carbonate (22 grams; 0.2 mole) and dimethylformamide (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated, with stirring, for a period of about 18 hours. After this time the reaction mixture-was filtered and then distilled to yield the desired product N-(l,3-'

dioxolan-2-ylmethyl)-2,6-diethylanilin'e.

I EXAMPLE 5 Preparation of N-a-Chloroacetyl-N-'( 1,3-dioxolan-2-ylmethyl )-2,6- diethylaniline N-( 1,3-dioxolan-2-ylmethyl)-2,6-diethylaniline 7.7

grams), sodium bicarbonate (6.0 grams), dioxane (20 ml) and water (4 ml) were charged into a glass reaction v' vessel equipped with a mechanical stirrer and thervmometer. This mixture was cooled to a temperature of about 0C and chloroacetylchloride (4.0 grams) was denser. Toluene sulfonic acid (0.3 grams) is addedto 5 the flask and the reaction mixture is refluxed fora riod of about 2 hours. After this time the reaction .rnix; ture is distilled under aspirator partial pressure-tore; v

- move methanol yielding the desired product 2-chloromethyll ,3-dioxolane.

' EXAMPLE '2 Preparation of N-( 1 ,3-Dioxolan-2-ylmethyl)-2,6-dimethylaniline 2,6-Dimethylaniline (75 grams), 2-chlor ornethyl- 133- added, with stirring, over a period of about 15 minutes. After the additionwas completed stirring was continued for a period of about 1 hour. After this time ether 1 ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over. anhydrous magnesium sulfate and stripped of solventsleaving a solid residue. The residue was recrystallized from'fan -e'thfei' -pentane mixture to yield the desired N a-chloroacetyl-N-(ljdioxolan;- 2 -ylmethyl)2,6-d ethylaniline having a melt;

EXAMPLE 6 Preparation of N-( 1 ,3-Dioxolan-2-ylmethyl)2-methyl-5chloroaniline 2-l\ lethyl-5chloroaniline (75 grams), 2-chloromethyll ,3-dioxolane (25 grams), potassium carbonate (22 grams) and dimethylformamide (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, and reflux condenser. The reaction mixture was heated, with stirring, for a period of about 26 hours. After this time the reac tion mixture was filtered and then distilled to yield the desired product N-(l,3-dioxolan-2-ylmethyl)2-methyl-5-chloroaniline having a boiling point of 1 16 to 118C at 0.1 mm of Hg pressure.

EXAMPLE 7 Preparation of N-oz-Chloroacetyl-N-( 1,3dioxolan-2ylrnethyl)-2- methyl-S-chloroaniline N-( 1,3-l)ioxolan-2-ylmethyl)-2-methyl-5- chloroaniline (8 grams), sodium bicarbonate (7 grams), dioxane (50 m1) and water (4 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. This mixture was cooled to a temperature of about 0C and chloroacetyl chloride (4.3 grams) was added, with stirring, over a period of about 15 minutes. After the addition was completed stirring was continued for a period of about 1 hour. After this time ether (100 ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue was recrystallized from hexane to yield the desired product N-oz-chloroacetyl- N-(1,3-dioxolan-2-ylmethyl)-2-methyl-5-chloroaniline having a melting point of 88 to 89C.

EXAMPLE 8 Preparation of 2-Chloromethyll ,3-dithiepane The dimethyl acetal of 2-chloroacetaldehyde (125 grams; 1.0 mole) and butandithiol-1,4 (122 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 2 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyl-1,3dithiepane.

EXAMPLE 9 Preparation of N-( l ,3Dithiepan-2'ylmethyl)-2,6-diethylaniline 2,6-1Diethylaniline (75 grams), 2-chloromethyl-1,3- dithiepane (36.5 grams), potassium carbonate (34 grams) and dimethylformamide (75 m1) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 18 hours. After this time the mixture is filtered and distilled to yield the desired product N-(l,3-dithiepan-2- ylmethyl)-2,6-diethylaniline.

EXAMPLE 10 Preparation of N-a-Ch1oroacetyl-N-( l ,3-dithiepan-2-ylmethyl)-2,6- diethylaniline N-(1,3-Dithiepan-2-y1methyl)-2,6-diethylaniline grams), sodium bicarbonate (10 grams), dioxane (3O ml) and water (5 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0C and chloroacetyl chloride (7 grams) is 5 added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether (100 ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of so]- vents leaving a solid residue. The residue is recrystaL lized to yield the desired product N-a-chloroacetyl-N- 1,3-dithiepan-2-ylmethyl)-2,6-diethylaniline.

EXAMPLE 11 Preparation of 2-Chloromethyl-l ,3 dioxane The dimethyl acetal of 2-chloroacetaldehyde (125 grams; 1.0 mole) and propandiol-1,3 (76 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 3 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyl-1,3-dioxane.

EXAMPLE 12 EXAMPLE 13 Preparation of N-a-Chloroacetyl-N-( 1,3-dioxan-2-ylmethyl )-2,6- diethylaniline N-(1,3-lDioxan-2-ylmethyl)-2,6-diethylaniline (25 grams), sodium bicarbonate (10 grams), dioxane (30 ml) and water (4 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0C and chloroacetyl chloride (15 grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether 100 ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the desired product N-a-chloroacetyl-N- l,3-dioxan-2-ylmethyl)-2,6-diethylaniline.

EXAMPLE 14 Preparation of 2-Chloromethyl-l,3-dioxepane The dimethyl acetal of 2-chloroacetaldehyde (125 grams; 1.0 mole) and butandiol-l,4 (90 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 3 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyll ,3-dioxepane.

EXAMPLE Preparation of N-( l ,3-Dioxepan-2-ylmethyl)-2,6-diethylaniline 1 2,6-Diethylaniline (75 grams), 2-chloromethyl-l,3-i dioxepane (15 grams), potassium carbonate (34 grams) and dimethylformamide (60 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 18 hours. After this time the mixture is filtered and distilled to yield the desired product N-(l,3-dioxepa'n-2- ylmethyl) 2,6-diethylaniline.

EXAMPLE 16 Preparation of f Nj-d-C-hloroacetyl-N-( 1 ,3-dioxepan-2-ylmethyl)-2,6-

diethylaniline N -(-1,3 'dioxepan-lylmethyl)-2,6-diethylaniline (2 65.3 'g rams), 'sodium bicarbonate (15 grams), dioxane (30 inl) and water (4 ml) are charged into a glass reaction vessel equipped witha mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0C and chloroacetyl chloride (15 grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about l' hour. After this time ether 100 ml) is added tot h e mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the" desired product N-a-chloroacetyl-N- 1 ,3-dioxepan 2-ylmethyl)-2,6-diethylaniline.

Additional compounds within the scope of the present invention can be prepared by the procedures detailed in the foregoing examples. In the following examples are given the essential starting materials required to prepare the indicated named compounds by the methods heretofore described.

v EXAMPLE 17 The dimethyl acetal of 2-chloroacetaldehyde ethandiol-LZ -+methylaniline chloroacetyl chloride methylaniline. v

' EX MPLE 18 EXAMPLE 22 The dimethyl acetal of 2-chloroacetaldehyde pentandiol-l ,2 2,4,6-tributylaniline chloroacetyl chloride N-oz-chloroac'etyl-N-(4-propyl-l,3-dioxolan-2- ylmethyl) 2,4,6-tributylaniline.

EXAMPLE 23 The dimethyl acetal of 2-chloroacetaldehyde hexandiol-1,2 2 -methyl-6-methoxyaniline a-chloroacetyl chloride dioxolan-2-ylmethyl)-2-methyl-6-methoxyaniline.

EXAMPLE 24 V The dimethyl acetal of 2-chloroacetaldehyde hexandiol-3,4 2,3-diethyl-6-ethoxyaniline a-chlorobutanoyl chloride N-a-chlorobutanoyl-N-(4,5-diethyl l ,3-dioxolan-2-ylmethyl )-2,3-diethyl-6-ethoxyaniline.

EXAMPLE 25 The dimethyl acetal of 2-chloroacetaldehyde propandiol-l,3 2-methyl-4-iodoaniline iodoacetyl chloride N-a-iodoacetyl-N-( l,3-dioxan-2-ylmethyl)-.

2-methyl-4-iodoaniline.

' EXAMPLE 26 The dimethyl acetal of 2-chloroacetaldehyde butandiol-l ,3+ 2-methyl-6-butoxyaniline chloroace chloride N-'a-chloroacetyl-N-( 1,3-dioxolan-2-ylmethyl)-2- The dimethyl acetal of 2-chloroacetaldehy de I ethandiol-l ,2 2-ethylaniline chloroace tyl chloride N-a-chloroacetyl-N-( l ,3-dioxolan-2-ylmethyl )-2-. 'ethylaniline.

EXAMPLE 19 tyl chloride N-a-chloroacetyl-N-(4-methyl-1,3- dioxan-2-ylmethyl )-2-methyl-6-butoxyaniline.

EXAMPLE 27 g The dimethyl acetal of 2-chloroacetaldehyde -l H butandiol-1,4 2-propyl-4-ethylaniline la-chlor'ohex- N-a-chlorohexanoyl-N-( 1,3

anoyl chloride dioxepan-2-ylmethyl )-2-propyl-4-ethylaniline.

EXAMPLE 28 The dimethyl acetal of 2-chloroacetaldehyde ethandithiol-l,2 2,6-dimethylaniline chloroacetyl ylmethyl)-2,6-dimethylanilinel EXAMPLE 29 The dimethyl acetal of -2-chloroacetaldehyde propandithiol-1,3 2,6-diethylan'ilir1e chloroacetyl A N-a-chloroacetyl-N-( 1 ,3-dithian-2- chloride ylmethyl)-2,6 diethylaniline.

For practical use as herbicides the compounds of this I invention are generally incorporated into herbicidal The dimethyl acetal of 3-chloropropionaldehyde ethandiol-l ,2 2,6-diethylaniline chloroacetyl chloride 2,6-diethylaniline.

EXAMPLE 20 I l f The dimethyl acetal'of2-chloroacetaldehyde propandiol-1,2 2,4-dimethylaniline bromoacetyl chloride N-a-bromoacetyl-N-(4-methyl-l,3-dioxolan-2- ylmethyl )-2,4-climethylaniline.

N-a-chloroacetyl-N-( 1 ,3-dioxolan-2-ylethyl)- compositions which comprise an inert carrier and a herbicidally toxic amount of such a compound. Such.

herbicidal compositions, which can also be called formulations, enable the active compound to be applied conveniently tothe site of the weed infestation in any desired quantity. These compositions can be solids such as dusts, granules, or wettable'powders; or they can be liquids such as solutions, aerosols, or emulsifiable concentrates.

For example, dusts canbe prepared by grinding and blending the active compound witha solid inert carrier N-a-chloroacetyl-N-( 1 ,3-dithiolan-2- such as the tales, clays, silicas, pyrophyllite, and the like. Granular formulations can be prepared by impregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculites, usually of a particle size range of from about 0.3 to 1.5 mm. Wettable powders, which can be dispersed in water or oil to any desired concentration of the active compound, can be prepared by incorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in common organic solvents such as kerosene or xylene so that they can be used directly as solutions in these solvents. Frequently, solutions of herbicides can be dispersed under super-atmospheric pressure as aerosols. However, preferred liquid herbicidal compositions are emulsifiable concentrates, which comprise an active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concentrates can be extended with water and/or oil to any desired concentration of active compound for application as sprays to the site of the weed infestation. The emulsifiers most commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion (water in oil) can be prepared for direct application to weed infestations.

A typical herbicidal composition according to this invention is illustrated by the following example, in which the quantities are in parts by weight.

The above ingredients are mixed in a mechanical grinder-blender and are ground until a homogeneous, free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application to the site of the weed infestation.

The compounds of this invention can be applied as herbicides in any manner recognized by the art. One method for the control of weeds comprises contacting the locus of said weeds with a herbicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity which is herbicidally toxic to said weeds, a compound of the present invention. The concentration of the new compounds of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about 95 percent by weight of the active compounds of this invention. in a preferred embodiment of this invention, the herbicidal compositions will comprise from about to about 75 percent by weight of the active compound. The compositions can also comprise such additional substances as other pesticides, such as insecticides, nematocides, fun gicides, and the like; stabilizers, Spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5 to about of the active ingredients in the herbicidal compositions. Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide herbicidal compositions which are more effective in controlling weeds and often provide results unattainable with separate compositions of the individual herbicides. The other herbicides, defoliants, dessicants and plant growth inhibitors, with which the compounds of this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-lD, 2,4,5-T, lVlClPA, MCIPB, 4(2,4-DB), 2,4-DE1B, 4-ClPB, 4-CPA, 4-ClP'P, 2,4,5-TlB, 2,4,5-T1ES, 3,4-DA, silvex and the like; carbamate herbicides such as UPC CIlPC, swep, barban, BClPC, ClElPC, CPlPC, and the like; thiocarbamate and dithiocarbamate herbicides such as CDEC, metham sodium, lEPTC, diallate, PEBC, perbulate, vernolate and the like; substituted urea herbicides such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and the like; symmetrical triazine herbicides such as simazine, chlorazine, atraone, desmetryne, norazine. ipazine, prometryn, atazine, trietazine, simetone, prometone, propazine, ametryne and the like; chloroacetamide herbicides such as alpha-chloro-N, N- dimethylacetamide, CDEA, CDAA, alpha-chloro-N- isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4-(chloroacetyl)morpholine, 1- (ehloroacetyl)piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3- dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, tricamba, amiben, fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy 3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3- nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin, bensulide, AMS, bromacil, 2-(3,4-dichlorophenyl)-4-methyl- 1,2,4-oxadiazolidine-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMIF, cypromid, DCB, DCPA, dichlone, diphenatril, DMTT, DNAIP, lEBlElP, EXD, HCA, ioxynil, lPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, h/lH, molinate, NlPA, OCH, paraquat, PCP, picloram, DPA, iPCA, pyrichlor, sesone, terbacil, terbutol, TCBA, brominil, (1 50144, l-ll-l76-l, l-l-732, lVl-2901, planavin, sodium tetraborate, calcium cyanamid, lDElF, ethyl xanthogen disulfide, sindone, sindone B, propanil and the like.

Such herbicides can also be used in the methods and compositions of this invention in the form of their salts, esters, amides, and other derivatives whenever applicable to the particular parent compounds.

Weeds are undesirable plants growing where they are not wanted, having no economic value, and interfering with the production of cultivated crops, with the growing of-ornamental plants, or with the welfare of livestock. Many types of weeds are known, including annuals such as pigweed, lambsquarters, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose-grass,

wheat, kochia, medic, com cockle, ragweed, sowthistle, coffeeweed, croton, cuphea; dodder, fumitory,

12 of hardy perennialweeds growing under favorable conditions. v

The herbicidal activity of the compounds of this invention was demonstrated by experiments carried out tively non-toxic to many beneficial plants. The exact amount of compound required will depend on a variety F hemp nettle p Spurry emex for the tire-emergence control of a variety of weeds. In Jungle pondweed fennel g these experiments small plastic greenhouse pots filled mg q i i blennials with dry soil were seeded with the weed seeds. Twentyf as Yi s F wild barley: fi four hours or less after seeding the pots were sprayed c ,amoml m mutlemroundleaved mallow bu with'water until the soil was wet and the test comf -IQP moth muuem and purple fi pounds formulated as aqueous emulsions of acetone thlsflei or perenmals such as whte Cockle pererlmal solutions containing emulsifiers weresprayed at the inryegra5S1 quackgrasst Johnson grass Canada thlsfle dicated concentrations on the surface of the soil. hedge bmdweed, Bermuda grass, sheep sorrel, curly v dock, nutgrass, field chickweed, dandelion, campanula, After spraying, the soil containers were placed in the field bindweed, Russian knapweed, mesquite, toadflax, greenhouse and provided with supplementary heat as yarrow, aster, gromwell, horsetail, ironweed, sesbania, required and daily or more frequent watering. The bulrush, cattail and wintercress. plants were maintained under these conditions for a pe- Similarly, such weeds can be classified as broadleaf riod of from -to days, at which time the condition or grassy weeds. It is economically desirable to control of the plants and the degree of injury to the plants was TABLE I Concentration of Test Yellow Johnson 7 Yellow Bamyard- Test Compound Compound in lbs/acre Nutsedge Grass Pigweed Foxtail grass Crabgrass I Product of l0 l0 9 l0 l0 l0 10 Example 3 t 4 10 9 t 10 9 1o 10 2 l0 l0 l0 9 9 l0 1 l0 8 l0 8 9 9 Product of l0 l0 9 l0 l0. l0 10 Example 5 a 4 l0 9 9 9 l0 9 2 l0 8 9 9 9 9 i 1 10 8' 3 9 8 9 Product of IO 9 2 l0 l0 l0 5 Example 18 4 l0 1 l0 9 9 7 2 l0 0 9 9 8 5 1 l0 0 3 8 4 4 the growth of such weeds without damaging beneficial rated on a scale of from 0 to 10, as follows: 0 no inplants or livestock. jury, 1,2 slight injury, 3,4 moderate injury, 5,6 The new compounds of this invention are particularly m r t ly Severe nj ry, .89 severe nj y n 0 valuable for weed control because they are toxic to The effectiveness of these compounds is many species and groups of weeds while they are rela- Onstrated y the following a We claim: 1. A compound of the formula of factors, including the hardiness of the particular weed species, weather, type of soil, method of application, the kind of beneficial plants in the same area, and the like. Thus, while the application of up to only about 1 or 2 ounces of active compound peracre may be suf ficient for good control of a light infestation of weeds growing under adverse conditions, the application of 10 pounds or more of an active compound per acre may be required for good control of a dense infestation wherein Y is selected from the group consisting of hydrogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R is lower alkyl; R, R, R", R and R are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen; m is the integer 2; Z and Z are sulfur; andn is an integer from 1 to 2.

2. The compound of claim 1, N-a-chloroacetyl-N- l,3-dithiepan-2-ylmethyl)-2,6-diethylaniline.

l l l i i 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1, N- Alpha -chloroacetyl-N-(1,3-dithiepan-2-ylmethyl)-2,6-diethylaniline. 